Bismuth oxyhalides (BiOXs, X = Cl, Br and I) are emerging photocatalytic materials with unique layered structure, flexible band structure and superior photocatalytic activity. The purpose of this study was to develop a facile alcoholysis route to prepare BiOClxI1-x nanosheet solid solutions at room temperature. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), photoluminescence emission spectroscopy (PL) and Brunauer-Emmett-Teller (BET) surface area analyzer were used to characterize the as-prepared photocatalysts. These results revealed that two-dimension BiOClxI1-x nanosheet solid solutions could be obtained with high percentage of {001} crystal facets exposed. Moreover, the formation of solid solution could regularly change the optical absorption thresholds and band gaps of BiOClxI1-x photocatalysts. The photocatalytic experiments indicated that BiOCl0.75I0.25 exhibited the highest photocatalytic performance for the degradation of Rhodamine B (RhB) under simulated sunlight irradiation and the photocatalytic process followed a pseudo-first-order kinetic equation. A possible mechanism of RhB photodegradation over BiOClxI1-x solid solutions was proposed based on the structural properties of BiOClxI1-x solid solutions and RhB photosensitization.